Low-haze transparent conductors

ABSTRACT

This disclosure is related to low-haze transparent conductors, ink compositions and method for making the same.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.16/026,019, filed Jul. 2, 2018, now pending, which is a divisional ofU.S. patent application Ser. No. 13/007,305, filed on Jan. 14, 2011, nowissued as 10,026,518, which claims the benefit of U.S. ProvisionalPatent Application No. 61/295,634, filed Jan. 15, 2010. U.S. patentapplication Ser. Nos. 16/026,019 and 13/007,305 and U.S. ProvisionalPatent Application No. 61/295,634 are incorporated herein by referencein their entireties.

BACKGROUND Technical Field

This disclosure is related to low-haze transparent conductors, and inkcompositions and method for making the same.

Description of the Related Art

Transparent conductors are optically clear and electrically conductivefilms. They are in widespread use in areas of display, touch-panel,photovoltaic (PV), various types of e-paper, electrostatic shielding,heating or anti-reflective coatings (e.g., windows), etc. Varioustechnologies have produced transparent conductors based on one or moreconductive media such as metallic nanostructures, transparent conductiveoxides (e.g., via sol-gel approach), conductive polymers, and/or carbonnanotubes. Generally, a transparent conductor further includes atransparent substrate on which the conductive film is deposited orcoated.

Depending on the end use, transparent conductors can be created withpredetermined electrical and optical characteristics, including, forexample, sheet resistance, optical transparency, and haze. Often,production of transparent conductors requires balancing trade-offsbetween the electrical and optical performances. As a general rule fornanostructure-based transparent conductors, higher transmission andlower haze are typically associated with fewer conductivenanostructures, which in turn results in a higher sheet resistance(i.e., less conductive).

Many commercial applications for transparent conductors (e.g.,touch-panels and displays) require the haze level be maintained below2%. Productions of low-haze transparent conductors are thus particularlychallenging because, in achieving such low level of haze, satisfactoryconductivity can be impossible to maintain.

BRIEF SUMMARY

Described herein are low-haze transparent conductors having a haze ofless than 1.5%, more typically, less than 0.5%, while maintaining highelectrical conductivities (e.g., less than 350 ohms/square), and methodsof making the same.

One embodiment provides a transparent conductor comprising a pluralityof conductive nanostructures, wherein the transparent conductor has ahaze of less than 1.5%, and a sheet resistance of less than 350ohms/square.

A further embodiment provides a transparent conductor wherein the sheetresistance is less than 50 ohms/square.

A further embodiment provides a transparent conductor wherein the hazeis less than 0.5%.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.3-0.4% and a sheet resistance is about170-350 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.4-0.5% and a sheet resistance is about120-170 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.5-0.7% and a sheet resistance is about80-120 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.7-1.0% and a sheet resistance is about50-80 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 1.0-1.5% and a sheet resistance is about30-50 ohms/square.

Further embodiments provide transparent conductors having the above filmspecifications, wherein more than 99% of the conductive nanostructureswith aspect ratios of at least 10 are no more than 55 μm long, orwherein more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 45 μm long, or wherein more than95% of the conductive nanostructures with aspect ratios of at least 10are about 5 to 50 μm long, or wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 5 to 30 μmlong, or wherein the conductive nanostructures with aspect ratios of atleast 10 have a mean length of about 10-22 μm, or wherein the conductivenanostructures with aspect ratios of at least 10 have a mean lengthsquared of about 120-400 μm².

Further embodiments provide transparent conductors having the above filmspecifications, wherein more than 99% of the conductive nanostructureswith aspect ratios of at least 10 are no more than 55 nm in diameter; orwherein more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 45 nm in diameter, or whereinmore than 95% of the conductive nanostructures with aspect ratios of atleast 10 are about 15 to 50 nm in diameter, or wherein more than 95% ofthe conductive nanostructures with aspect ratios of at least 10 areabout 20 to 40 nm in diameter, or wherein the conductive nanostructureswith aspect ratios of at least 10 have a mean diameter of about 26-32 nmand a standard deviation in the range of 4-6 nm, or wherein theconductive nanostructures with aspect ratios of at least 10 have a meandiameter of about 29 nm and a standard deviation in the range of 4-5 nm.

Further embodiments provide transparent conductors having the above filmspecifications, wherein more than 99% of the conductive nanostructureswith aspect ratios of at least 10 are no more than 55 μm long, and morethan 99% of the conductive nanostructures with aspect ratios of at least10 are no more than 55 nm in diameter; or wherein more than 95% of theconductive nanostructures with aspect ratios of at least 10 are about 5to 50 μm long, and more than 95% of the conductive nanostructures withaspect ratios of at least 10 are about 15 to 50 nm in diameter; orwherein more than 95% of the conductive nanostructures with aspectratios of at least 10 are about 5 to 30 μm long, and more than 95% ofthe conductive nanostructures with aspect ratios of at least 10 areabout 20 to 40 nm in diameter; or wherein the conductive nanostructureswith aspect ratios of at least 10 have a mean length of about 10-22 gm,and wherein the conductive nanostructures with aspect ratios of at least10 have a mean diameter of about 26-32 nm and a standard deviation inthe range of 4-6 nm; or wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 45 gmlong, and more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 45 nm in diameter.

A further embodiment provides a method comprising: growing metalnanowires from a reaction solution including a metal salt and a reducingagent, wherein the growing includes:

reacting a first portion of the metal salt and the reducing agent in thereaction solution for a first period of time, and

gradually adding a second portion of the metal salt over a second periodof time while maintaining a substantially constant concentration of lessthan 0.1% w/w of the metal salt in the reaction solution.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 55 μmlong, a viscosity modifier, a surfactant; and a dispersing fluid.

Additional embodiments provide ink compositions wherein more than 99% ofthe conductive nanostructures with aspect ratios of at least 10 are nomore than 45 μm long; or wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 5 to 50 μmlong; or wherein more than 95% of the conductive nanostructures withaspect ratios of at least 10 are about 5 to 30 μm long; or wherein theconductive nanostructures with aspect ratios of at least 10 have a meanlength of about 10-22 μm; or wherein the conductive nanostructures withaspect ratios of at least 10 have a mean length squared of about 120-400μm².

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 55 nmin diameter; a viscosity modifier; a surfactant; and a dispersing fluid.

Additional embodiments provide ink compositions wherein more than 99% ofthe conductive nanostructures with aspect ratios of at least 10 are nomore than 45 nm in diameter; wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 15 to 50 nmin diameter; wherein more than 95% of the conductive nanostructures withaspect ratios of at least 10 are about 20 to 40 nm in diameter; whereinthe conductive nanostructures with aspect ratios of at least 10 have amean diameter of about 26-32 nm and a standard deviation in the range of4-6 nm; wherein the conductive nanostructures with aspect ratios of atleast 10 have a mean diameter of about 29 nm and a standard deviation inthe range of 4-5 nm.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, composition comprising: a plurality ofconductive nanostructures; a viscosity modifier; a surfactant; and adispersing fluid, wherein more than 99% of the conductive nanostructureswith aspect ratios of at least 10 are no more than 55 μm long, and morethan 99% of the conductive nanostructures with aspect ratios of at least10 are no more than 55 nm in diameter.

Additional embodiments provide ink compositions, wherein more than 95%of the conductive nanostructures with aspect ratios of at least 10 areabout 5 to 50 μm long, and more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 15 to 50 nmin diameter; or wherein more than 95% of the conductive nanostructureswith aspect ratios of at least 10 are about 5 to 30 μm long, and morethan 95% of the conductive nanostructures with aspect ratios of at least10 are about 20 to 40 nm long; or wherein the conductive nanostructureswith aspect ratios of at least 10 have a mean length of about 10-22 μm,and wherein the conductive nanostructures with aspect ratios of at least10 have a mean diameter of about 26-32 nm and a standard deviation inthe range of 4-6 nm; or wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 45 μmlong, and more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 45 nm in diameter.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

In the drawings, identical reference numbers identify similar elementsor acts. The sizes and relative positions of elements in the drawingsare not necessarily drawn to scale. For example, the shapes of variouselements and angles are not drawn to scale, and some of these elementsare arbitrarily enlarged and positioned to improve drawing legibility.Further, the particular shapes of the elements as drawn are not intendedto convey any information regarding the actual shape of the particularelements, and have been selected solely for ease of recognition in thedrawings.

FIG. 1 is a histogram displaying the distribution profile of apopulation of nanowires according to their lengths.

FIG. 2 is a histogram displaying the distribution profile of apopulation of nanowires according to their diameters.

FIG. 3 is a flow chart of a two-phase reaction scheme for preparingsilver nanowires that conform to certain size distribution profiles.

FIG. 4 shows the effect of purification on the diameter distribution ofsilver nanowires prepared by a two-phase reaction.

FIG. 5 illustrates the length distribution profiles of three batches ofsilver nanowires as log normal distributions.

FIG. 6 illustrates the diameter distribution profiles of three batchesof silver nanowires as normal or Gaussian distributions.

FIG. 7 shows an inverse correlation of the haze and the resistance ofconductive thin films formed of silver nanowires.

FIG. 8 shows a positive correlation of the transmission and theresistance of conductive thin films formed of silver nanowires.

DETAILED DESCRIPTION OF THE INVENTION

Generally speaking, the transparent conductors described herein are thinconductive films of conductive nanostructures. In the transparentconductor, one or more electrically conductive paths are establishedthrough continuous physical contacts among the nanostructures. Aconductive network of nanostructures is formed when sufficientnanostructures are present to reach an electrical percolation threshold.The electrical percolation threshold is therefore an important valueabove which long range connectivity can be achieved.

The electrical conductivity of the conductive film is often measured by“film resistance,” “resistivity” or “sheet resistance,” which isrepresented by ohm/square (or “Ω/□”). The film resistance is a functionof at least the surface loading density, the size/shapes of thenanostructures, and the intrinsic electrical property of thenanostructure constituents. As used herein, a thin film is consideredconductive if it has a sheet resistance of no higher than 10⁸ Ω/□.Preferably, the sheet resistance is no higher than 10⁴ Ω/∪, 3,000 Ω/∪,1,000 Ω/□ or 350 Ω/∪, or 100 Ω/□. Typically, the sheet resistance of aconductive network formed by metal nanostructures is in the ranges offrom 10 Ω□ to 1000 Ω/□, from 100 Ω/□ to 750 Ω/□, 50 Ω/□ to 200 Ω/∪, from100 Ω/∪, or from 100 Ω∪ to 250 Ω/∪, or 10 Ω/∪ to 200 Ω/∪, from 10 Ω/□to50 Ω/□, or from 1 Ω/□ to 10 Ω/□.

Optically, the nanostructure-based transparent conductors have highlight transmission in the visible region (400-700 nm). Typically, thetransparent conductor is considered optically clear when the lighttransmission is more than 85% in the visible region. More typically, thelight transmission is more than 90%. or more than 93%, or more than 95%.

Haze is another index of optical clarity. It is generally recognizedthat haze results from light scattering and reflection/refraction due toboth bulk and surface roughness effects. Low-haze transparent conductorsare particularly desirable in applications such as touch screens anddisplays, in which optical clarity is among critical performancefactors.

For transparent conductors in which nanostructures form the conductivemedia, light scattering arising from the nanostructures is inevitable.However, as described herein, low-haze transparent conductors can beobtained by controlling the size distribution profile and particlemorphology of the nanostructures.

Generally, the level at which haze can be detected by the human eye isabout 2%. Thus, various embodiments of this disclosure are directed totransparent conductors having less than 1.5% in haze.

One embodiment provides a transparent conductor comprising a pluralityof conductive nanostructures, wherein the transparent conductor has ahaze of less than 1.5%, and a sheet resistance of less than 350ohms/square.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze of less than 1.5%, and a sheet resistance of lessthan 50 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze of less than 0.5%, and a sheet resistance of lessthan 350 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze of less than 0.3%, and a sheet resistance of lessthan 350 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.3-0.4% and a sheet resistance is about170-350 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.4-0.5% and a sheet resistance is about120-170 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.5-0.7% and a sheet resistance is about80-120 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 0.7-1.0% and a sheet resistance is about50-80 ohms/square.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures, wherein the transparentconductor has a haze is about 1.0-1.5% and a sheet resistance is about30-50 ohms/square.

Nanostructure Size Distribution Profile

In order to meet the above thin film specifications, includingtransmission, sheet resistance and haze, the transparent conductorcomprises nanostructures that conform to certain size distributionprofiles.

As used herein, “conductive nanostructures” or “nanostructures”generally refer to electrically conductive nano-sized structures, atleast one dimension of which (i.e., width) is less than 500 nm, moretypically, less than 100 nm or 50 nm, even more typically, in the rangeof 20 to 40 nm. Lengthwise, the nanostructures are more than 500 nm, ormore than 1 μm, or more than 10 μm in length. More typically, thenanostructures are in the range of 5 to 30 μm long.

The nanostructures can be of any shape or geometry. One way for definingthe geometry of a given nanostructure is by its “aspect ratio,” whichrefers to the ratio of the length and the width (or diameter) of thenanostructure. In certain embodiments, the nanostructures areisotropically shaped (i.e., aspect ratio=1). Typical isotropic orsubstantially isotropic nanostructures include nanoparticles. Inpreferred embodiments, the nanostructures are anisotropically shaped(i.e. aspect ratio≠1). The anisotropic nanostructure typically has alongitudinal axis along its length. Exemplary anisotropic nanostructuresinclude nanowires (solid nanostructures having aspect ratio of at least10, and more typically, at least 50), nanorods (solid nanostructureshaving aspect ratio of less than 10) and nanotubes (hollownanostructures).

In addition to the loading density of the nanostructures, their sizesand shapes are among factors that determine the film specifications.More specifically, the length, width and aspect ratio of thenanostructures, often to different degrees, affect the final sheetresistance (R), transmission (T) and haze (H). For instance, the lengthsof the nanostructures typically control the extent of theinterconnectivity of the nanostructures, which in turn affect the sheetresistance of the transparent conductor. The widths of thenanostructures do not typically affect the interconnectivity of thenanostructure; however, they can significantly impact the haze of thetransparent conductor.

Realistically, rather than having a uniform size, a given population ofnanostructures (e.g., the product following synthesis and purification)includes nanostructures in a range of sizes (length and width).Accordingly, the specifications (R, T and H) of a thin film formed bysuch a population of nanostructures depend on the collectivecontribution of nanostructures across a size distribution profile.

A size distribution profile comprises a set of values that define therelative amounts or frequencies of nanostructures present, sortedaccording to their respective sizes (length and width).

The size distribution profile can be graphically represented by ahistogram, which is created by sorting a given population ofnanostructures according to non-overlapping, regular intervals ofcertain size range and plotting the frequencies of nanostructures thatfall within each interval. The regular interval of the size range isalso referred to as “bin range.”

FIG. 1 is a histogram displaying the distribution profile of apopulation of nanostructures (e.g., nanowires) according to theirlengths, with the bin ranges (5 μm intervals) on the X axis and thefrequencies as columns along the Y axis. Given the lengths andcorresponding frequency data, a smooth curve can also be constructedbased on a probability density function. FIG. 1 thus quantitatively andgraphically shows the shape (a log normal distribution) and spread(variations around the mean) of the length distribution in saidpopulation of nanostructures.

Moreover, FIG. 1 shows the maximum and minimum lengths of the range ofthe lengths. It can be observed that certain nanostructures thatcontribute to light scattering without contributing to conductivity arepresent at much lower frequencies (e.g., less than 10%, or moretypically, less than 5%) in the size distribution profile. Thesenanostructures are seen as “bright objects” due to their appearance ondark field micrographs. These bright objects include, for example,nanostructures that are too wide and/or too short (e.g., nanoparticles,nanorods) to effectively participate in the electrical percolationprocess. Some or all of these bright objects have low aspect ratios(less than 10).

Thus, one embodiment provides a low-haze transparent conductorcomprising a plurality of conductive nanostructures and having a haze ofless than 1.5%, and sheet resistance of less than 350 ohms/square,wherein more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 55 μm long.

A further embodiment provides a low-haze transparent conductorcomprising a plurality of conductive nanostructures and having a haze ofless than 1.5%, wherein more than 99% of the conductive nanostructureswith aspect ratios of at least 10 are no more than 45 μm long.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein more than 95% of the conductive nanostructures with aspectratios of at least 10 are about 5 to 50 μm long.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein more than 95% of the conductive nanostructures with aspectratios of at least 10 are about 5 to 30 μm long.

In addition to the length distribution, mean length (<l>) and meanlength squared (<l²>) of the nanostructures are also indicative of thefilm specifications. In particular, the mean length squared (<l²>) ofthe nanostructures determine the percolation threshold, and is thusdirectly related to the sheet resistance. Co-owned and co-pending U.S.application Ser. No. 11/871,053 provides more detailed analysis of thecorrelation between these two parameters with sheet resistance innanowire-based transparent conductors, which application is incorporatedherein by reference in its entirety.

As used herein, mean length (<l>) is the sum of all the measured lengthsdivided by the counted number of the nanostructures, as describedherein.

Mean length squared (<l²>) can be represented by:

${\langle I^{2}\rangle} = \frac{\sum\limits_{i = 1}^{n}I_{i}^{2}}{n}$

Thus, a further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein the conductive nanostructures with aspect ratios of at least 10have a mean length of about 10-22 μm.

In various further embodiments, the conductive nanostructures withaspect ratios of at least 10 have a mean length of about 12-20 μm, 14-18μm or 15-17 μm.

Another embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein the conductive nanostructures with aspect ratios of at least 10have a mean length squared of about 120-600 μm².

In various further embodiments, the conductive nanowires with aspectratio of at least 10 have a mean length squared of about 240-400 μm² or260-350 μm².

FIG. 2 is a histogram displaying the distribution profile of apopulation of nanostructures (e.g., nanowires) according to theirdiameters, with the bin ranges (5 nm intervals) on the X axis and thefrequencies as columns along the Y axis. Given the diameters andcorresponding frequency data, a smooth curve can also be constructedbased on a probability density function. FIG. 2 thus quantitatively andgraphically shows the shape (a normal or Gaussian distribution) andspread (variation around the mean) of the diameter distribution in saidpopulation of nanostructures.

As a result of the normal distribution, the distribution profile of theplurality of nanostructures can be defined by the mean and standarddeviation of the diameters.

FIG. 2 shows a narrow distribution (i.e., relatively small standarddeviation) of the diameters of the nanostructures. As used herein, anormal distribution is considered narrow when the standard deviation isless than 20% of the mean, or more typically less than 15% of the mean.It is believed that a narrow diameter distribution reduces thecompositional heterogeneity of the nanostructures of the film, resultingin a lowered haze.

Thus, one embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 55 nm in diameter.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 45 nm in diameter.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein more than 95% of the conductive nanostructures with aspectratios of at least 10 are about 15 to 50 nm in diameter.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein more than 95% of the conductive nanostructures with aspectratios of at least 10 are about 20 to 40 nm in diameter.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein the conductive nanostructures with aspect ratios of at least 10have a mean diameter of about 26-32 nm and a standard deviation in therange of 4-6 nm.

A further embodiment provides a transparent conductor comprising aplurality of conductive nanostructures having a haze of less than 1.5%,wherein the conductive nanostructures with aspect ratios of at least 10have a mean diameter of about 29 nm and a standard deviation in therange of 4-5 nm.

A further embodiment provides a low-haze transparent conductorcomprising a plurality of conductive nanostructures and having a haze ofless than 1.5%, wherein more than 99% of the conductive nanostructureswith aspect ratios of at least 10 are no more than 55 μm long, and morethan 99% of the conductive nanostructures with aspect ratios of at least10 are no more than 55 nm in diameter.

A further embodiment provides a low-haze transparent conductorcomprising a plurality of conductive nanostructures and having a haze ofless than 1.5%, wherein more than 99% of the conductive nanostructureswith aspect ratios of at least 10 are no more than 45 μm long, and morethan 99% of the conductive nanostructures with aspect ratios of at least10 are no more than 45 nm in diameter.

A further embodiment provides a low-haze transparent conductorcomprising a plurality of conductive nanostructures and having a haze ofless than 1.5%, wherein more than 95% of the conductive nanostructureswith aspect ratios of at least 10 are about 5 to 50 μm long, and morethan 95% of the conductive nanostructures with aspect ratios of at least10 are about 15 to 50 nm in diameter.

A further embodiment provides a low-haze transparent conductorcomprising a plurality of conductive nanostructures and having a haze ofless than 1.5%, wherein more than 95% of the conductive nanostructureswith aspect ratios of at least 10 are about 5 to 30 μm long, and morethan 95% of the conductive nanostructures with aspect ratios of at least10 are about 20 to 40 nm long.

A further embodiment provides a low-haze transparent conductorcomprising a plurality of conductive nanostructures and having a haze ofless than 1.5%, wherein the conductive nanostructures with aspect ratiosof at least 10 have a mean length of about 10-22 μm, and wherein theconductive nanostructures with aspect ratios of at least 10 have a meandiameter of about 26-32 nm and a standard deviation in the range of 4-6nm.

Additional embodiments provide that any of the low-haze transparentconductors described above have a haze of less than 1.0%, less than0.8%, or less than 0.6%, or less than 0.5%, or less than 0.4%, or lessthan 0.3%.

Additional embodiments provide that in any of the low-haze transparentconductors described above, the conductive nanostructures with aspectratios of at least 10 are nanowires, including without limitation, metalnanowires (e.g., silver nanowires), and metal nanotubes (e.g., silver orgold nanotubes).

Preparation of Nanostructures

The nanostructures (e.g., metallic nanowires) that conform to the sizedistribution profiles described herein can be prepared by chemicalsynthesis.

Conventionally, metallic nanowires can be nucleated and grown out of asolution of the corresponding metallic salt in the presence of anexcessive amount of reducing agent, which also serves as a solvent(e.g., ethylene glycol or propylene glycol). In this type of solutionphase reaction, the nanowire growth typically progresses simultaneouslyin the radial and axial directions. Accordingly, as the nanowireselongate, the diameters also enlarge. See, e.g., Y. Sun, B. Gates, B.Mayers, & Y. Xia, “Crystalline silver nanowires by soft solutionprocessing”, Nanolett, (2002), 2(2): 165-168.

For low-haze transparent conductors described herein, the nanowires canhave relatively small diameters (e.g., mean diameters of 15-50 nm) and anarrow width distribution. At these diameter ranges, conventionalsynthesis would have produced much shorter nanowires than the lengthdistribution (including mean length) that provides a satisfactoryconductivity (e.g., less than 350 ohm/square). Conversely, if thenanowires are allowed to grow to the requisite length to attain thesatisfactory conductivity, the diameters of the nanowires are inevitablylarge enough to raise the haze value (e.g., above 1.5%).

To provide a population of nanowires that conform to the sizedistribution profiles and thus form low haze transparent conductivefilms, a two-phase synthesis is described.

The two-phase synthesis separately promotes radial and axial growth ofthe nanowires, such that the diameter and length of the nanowires can beseparately controlled. FIG. 3 is a flow chart showing the two-phasepreparation of silver nanowires, which are nucleated and grown from apropylene glycol solution of silver nitrate. Additional components ofthe reaction include polyvinylpyrrolidone and tetra-n-butylammoniumchloride (TBAC). By controlling the amount and sequence of adding silvernitrate, the growth and the final size of the nanowires can becontrolled.

The silver nitrate solution contains a pre-determined total amount ofsilver nitrate, which is split into two portions to be added at twodifferent phases of the reaction. The split can be in the ranges of30-70: 70-30, and preferably at 50:50.

In the first phase of the reaction, a first portion of the total silvernitrate is used. Further, a fraction of the first portion of silvernitrate is introduced with TBAC, such that the concentration of theinitial silver ions in the reaction mixture is about 0.001 to 0.025%.Thereafter, the remainder of the first portion of the silver nitrate isadded. The first phase of the reaction typically is allowed to run for12-16 hours. During this phase, nanowires are formed as they grow inboth radial and axial directions. At the end of the first phase, thelengths of the nanowires are shorter than the final desired lengths;however, the diameters of the nanowires are substantially close to theirfinal dimensions.

In the second phase of the reaction, the second portion of the silvernitrate is gradually added over a period in which the concentration ofthe silver ions in the reaction solution is maintained substantiallyconstant and below 0.1% w/w. During the second phase, the predominantwire growth is in the axial direction, while the radial growth iseffectively slowed or even stopped.

The total reaction time of the two phases is about 24 hours. Thereaction can be quenched with de-ionized (DI) water, at which pointgrowth in all directions is arrested.

Throughout the reaction, the reaction mixture is preferably kept in aninert atmosphere. The inert gas may be a noble gas (e.g. helium, neon,argon, krypton or xenon) or other inert gas such as nitrogen or an inertgas mixture or compound gas. Typically, the reaction vessel is initiallypurged with an inert gas for a predetermined period of time. The purgingis maintained throughout the reaction. More detailed descriptionregarding purging can be found in co-pending and co-owned U.S.application Ser. No. 61/275,093, which application is incorporatedherein by reference in its entirety.

Thus, one embodiment provides a method comprising: growing metalnanowires from a reaction solution including a metal salt and a reducingagent, wherein the growing includes:

reacting a first portion of the metal salt with the reducing agent inthe reaction solution for a first period of time, and

gradually adding the second portion of the metal salt over a secondperiod of time while maintaining a substantially constant concentrationof less than 0.1% w/w of the metal salt in the reaction solution.

Further embodiments provide that the metal nanowires are silvernanowires, the metal salt is silver nitrate, and the reducing agent ispropylene glycol or ethylene glycol.

A further embodiment provides that the first and second portions of themetal salt are about equal amount.

Another embodiment provides that during the first period of time, afraction of the first portion of the metal salt is first added with anammonium salt (TBAC), followed by the remainder of the first portion ofthe metal salt. In some embodiments, the fraction represents about 0.6%of the total metal salt, and about 0.001 to 0.025% w/w of the metal ionsin the reaction mixture.

It should be understood that although nanowires (e.g., silver nanowires)are described in connection with the above two-phase synthesis,nanowires of other conductive material can be prepared in a similarmanner. Other metallic material can be an elemental metal (e.g.,transition metals) or a metal compound (e.g., metal oxide). The metallicmaterial can also be a bimetallic material or a metal alloy, whichcomprises two or more types of metal. Suitable metals include, but arenot limited to, silver, gold, copper, nickel, gold-plated silver,platinum and palladium.

Thin Film Preparation

In various embodiments, the transparent conductors described herein arethin films cast from dispersions of nanostructures, also referred to as“ink compositions.”

A typical ink composition for depositing metal nanowires comprises, byweight, from 0.0025% to 0.1% surfactant (e.g., a preferred range is from0.0025% to 0.05% for Zonyl® FSO-100 or 0.005% to 0.025% Triton X-100),from 0.02% to 4% viscosity modifier (e.g., a preferred range is 0.02% to0.5% for hydroxypropylmethylcellulose (HPMC), from 0.01 to 1.5% metalnanowires, and from 94.5% to 99.0% fluid (for dispersing or suspendingthe other constituents).

In various embodiments, ink compositions of silver nanowires include0.1% to 0.2% silver nanowires, 0.2 to 0.4% high purity HPMC, and 0.005%to 0.025% Triton X-100. Methods of purifying HPMC are described inco-pending and co-owned U.S. application Ser. No. 61/175,745, whichapplication is incorporated herein by reference in its entirety.

Representative examples of suitable surfactants includefluorosurfactants such as ZONYL® surfactants, including ZONYL® FSN,ZONYL® FSO, ZONYL® FSA, ZONYL® FSH (DuPont Chemicals, Wilmington, Del.),and NOVEC™ (3M, St. Paul, Minn.). Other exemplary surfactants includenon-ionic surfactants based on alkylphenol ethoxylates. Preferredsurfactants include, for example, octylphenol ethoxylates such asTRITON™ (x100, x114, x45), and nonylphenol ethoxylates such as TERGITOL™(Dow Chemical Company, Midland Mich.). Further exemplary non-ionicsurfactants include acetylenic-based surfactants such as DYNOL® (604,607) (Air Products and Chemicals, Inc., Allentown, Pa.) and n-dodecylβ-D-maltoside.

Examples of suitable viscosity modifiers include hydroxypropyl methylcellulose (HPMC), methyl cellulose, xanthan gum, polyvinyl alcohol,carboxy methyl cellulose, hydroxy ethyl cellulose. Examples of suitablefluids include water and isopropanol.

Thus, one embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 99% of the conductivenanostructures are no more than 55 μm long.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 99% of the conductivenanostructures are no more than 45 μm long.

A further embodiment an ink composition comprising a plurality ofconductive nanostructures, wherein more than 95% of the conductivenanostructures are about 5 to 50 μm long.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 5 to 30 μmlong.

a further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein the conductive nanostructures withaspect ratios of at least 10 have a mean length of about 10-22 μm.

Another embodiment provides an ink composition comprising a plurality ofconductive nanostructures, wherein the conductive nanostructures withaspect ratios of at least 10 have a mean length squared of about 120-400μm².

Another embodiment provides an ink composition comprising a plurality ofconductive nanostructures, wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 55 nmin diameter.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 45 nmin diameter.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 15 to 50 nmin diameter.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 20 to 40 nmin diameter.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein the conductive nanostructures withaspect ratios of at least 10 have a mean diameter of about 26-32 nm anda standard deviation in the range of 4-6 nm.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein the conductive nanostructures withaspect ratios of at least 10 have a mean diameter of about 29 nm and astandard deviation in the range of 4-5 nm.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 55 μmlong, and more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 55 nm in diameter.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 99% of the conductivenanostructures with aspect ratios of at least 10 are no more than 45 μmlong, and more than 99% of the conductive nanostructures with aspectratios of at least 10 are no more than 45 nm in diameter.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 5 to 50 μmlong, and more than 95% of the conductive nanostructures with aspectratios of at least 10 are about 15 to 50 nm in diameter.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein more than 95% of the conductivenanostructures with aspect ratios of at least 10 are about 5 to 30 μmlong, and more than 95% of the conductive nanostructures with aspectratios of at least 10 are about 20 to 40 nm long.

A further embodiment provides an ink composition comprising a pluralityof conductive nanostructures, wherein the conductive nanostructures withaspect ratios of at least 10 have a mean length of about 10-22 μm, andwherein the conductive nanostructures with aspect ratios of at least 10have a mean diameter of about 26-32 nm and a standard deviation in therange of 4-6 nm.

Further embodiments provide that in each of the above embodiments, thenanostructures are metal nanowires (e.g., silver nanowires).

The ink composition can be prepared based on a desired concentration ofthe total nanostructures (e.g., nanowires), which is an index of theloading density of the final conductive film formed on the substrate.

The substrate can be any material onto which nanowires are deposited.The substrate can be rigid or flexible. Preferably, the substrate isalso optically clear, i.e., light transmission of the material is atleast 80% in the visible region (400nm-700 nm).

Examples of rigid substrates include glass, polycarbonates, acrylics,and the like. In particular, specialty glass such as alkali-free glass(e.g., borosilicate), low alkali glass, and zero-expansion glass-ceramiccan be used. The specialty glass is particularly suited for thin paneldisplay systems, including Liquid Crystal Display (LCD).

Examples of flexible substrates include, but are not limited to:polyesters (e.g., polyethylene terephthalate (PET), polyesternaphthalate, and polycarbonate), polyolefins (e.g., linear, branched,and cyclic polyolefins), polyvinyls (e.g., polyvinyl chloride,polyvinylidene chloride, polyvinyl acetals, polystyrene, polyacrylates,and the like), cellulose ester bases (e.g., cellulose triacetate,cellulose acetate), polysulphones such as polyethersulphone, polyimides,silicones and other conventional polymeric films.

The ink composition can be deposited on the substrate according to, forexample, the methods described in co-pending U.S. patent applicationSer. No. 11/504,822.

Spin coating is a typical technique for depositing a uniform film on asubstrate. By controlling the loading amount, spin speed and time, thinfilms of various thicknesses can be formed. It is understood that theviscosity, the shear behavior of the suspending fluid as well as theinteractions between the nanowires, may affect the distribution andinterconnectivity of the nanowires deposited.

For example, the ink compositions described herein can be spin-coated ona glass substrate at a speed of 400-2000 rpm for 60 seconds, withacceleration 1000 rpm/s. The thin film can be further subjected tocertain post-treatments, including baking at 50° C. for 90 seconds and140° C. for 90 seconds. Pressure treatment with or without heat can befurther employed to adjust the final film specifications.

As understood by one skilled in the art, other deposition techniques canbe employed, e.g., sedimentation flow metered by a narrow channel, dieflow, flow on an incline, slit coating, gravure coating, microgravurecoating, bead coating, dip coating, slot die coating, and the like.Printing techniques can also be used to directly print an inkcomposition onto a substrate with or without a pattern. For example,inkjet, flexoprinting and screen printing can be employed.

Nanowires Size Measurement

The lengths and widths of the nanostructures (e.g., nanowires) as wellas their numbers can be measured and counted through a combination ofmicroscopy and software-assisted image analysis (e.g., available fromClemex Technologies Inc, Quebec, Canada). Regardless of the techniquesused for measurements and counting, the microscope system, includingoptics, camera, and image analysis software, are to be verified and/orcalibrated at regular intervals using an National Institute Standardsand Technology (NIST) traceable standard.

An optical microscope (e.g., Olympus BX51) equipped with a highresolution digital camera, Clemex stage, and Clemex Analysis softwaremay be used to measure the magnified images of the nanowires.

The lighting on the microscope should be adjusted such that eachnanostructure is clearly illuminated to emphasize the nanostructurecontrast relative to the background, such that that the image analysissoftware can accurately recognize and measure the nanostructures. Forinstance, the microscope may be set to dark field and focuses the imageon the monitor at 500× magnification. Each frame on the monitor may beset to represent an area of 258 μm×193 μm on the film.

The wire density should be such that the majority of wires are isolatedfrom each other and not overlapping. Overlapping can be managed orminimized when there are no more than 25 (or more typically no more than40) wires per frame. To reduce incidences of overlapping wires, theinitial dilute dispersion of nanowires can be diluted further. If thewires are too sparse (less than 5 per frame), then nanowireconcentration in the starting nanowire dispersion should be increased.Nanowires that touch or are truncated by the edge of the image areautomatically eliminated from the measurement using the image analysissoftware. In addition, bright objects, e.g., nanostructures havingaspect ratio of less than 10, are excluded from the measurements andcounting.

For instance, to measure the lengths of a population of nanowires, aninitial dilute dispersion of metal nanowires in isopropanol (about 0.001wt % metal) can be spin-coated on a 2″ by 2″ clean piece of glass at1000 rpm for 30 seconds. The film is dried thereafter.

The lengths of the nanowires may be measured by initiating a specialroutine or program using Clemex software:

Prolog 001 Edit Analysis Properties 002 Load Stage Pattern (should beused in Prolog only) File: length.stg Path: C:\IaFiles\Pattern End ofProlog 001 Grab 002 Top Hat on White ×8 Level: White Size: 8Reconstruction cycles: 4 Confidential TEST METHOD Page 3 of 3 003Relative Gray Threshold BPL1, C1(10.384-207.384), C2(0.000-0.000)Background: Black Mean Method: Mean + C1 + C2 * STD 004 Fill => BPL1Fill border objects : No 005 Trap BPLI -> None 6×6 006 Square Grid 1×1-> BPL8 Overall Grid Dimensions 1392 × 1040 pixels 258 × 193 μm 007Transfer (BPL1 SEL BPL8) -> None 008 Object Transfer BPL1 -> BPL2 AspectRatio greater than 3 009 Object Measures (BPL1, 2) -> OBJM1 StringLength Aspect Ratio String Length Squared 010 Clear => All Epilog 001Generate Report (should be used in Epilog only) Report Template:<<Default Folder|using:#9>>\test2.xlt Save Report: To “C:\Clemex\LengthAnalyses\<<Sample>>.xls” Overwrite Protection: Yes Print Report: NoClose Report: No 002 Save Analysis Results to LengthData.cxr'Destination: C:\Clemex\Length Analyses\clemex data files\LengthData.cxrOverwrite Protection: Yes Close after Saving: No End of Epilog

Lengths are automatically measured as the program goes through 144frames. After the measurement is completed, the Clemex software willproduce a statistical report containing all the key data (including meanlength, standard deviation, mean length squared and binned distributionof lengths). To accept results, the total wire count should be between800-6000 wires. If the wire count is outside of this range, the testmust be repeated with dilution adjustments to the initial nanowiredispersion. As discussed herein, bright objects, e.g., nanostructureshaving aspect ratio of less than 10, are excluded from the counting.

The widths of the nanowires are measured by Scanning Electron Microscope(SEM).

To prepare a sample, a few drops of a dilute nanowire dispersion inmethanol (˜0.05 wt % metal) are added on a clean aluminum SEM samplestage. Methanol is allowed to dry and the sample is rinsed several timeswith additional amounts of methanol to remove any organic residues fromthe nanowires. The sample is dried before it is inserted into an SEMinstrument (e.g., Hitachi S-4700 SEM, verified and/or calibrated atregular intervals using an NIST traceable standard).

The SEM beam acceleration voltage is set to around 10.0 kV. Typically, 8or more SEM photos at 60K to 80K are taken. Enough photos should betaken for measurement of at least 150 wires (typically 6-10 photos).

For accurate measurement and analysis, the nanowires should be separatedfrom each other in a thin layer and clear of any organic residue.Further, the images should be focused well.

After the SEM images are acquired, the photos are uploaded into theClemex Image Analysis software, programmed with a special analysisroutine:

001 Edit Analysis Properties End of Prolog 001 Load Image ‘*.TIF’  File:*.TIF  Path: C:\Clemex\SEM width photos  Use Default Calibration: No 002Relative Gray Threshold  BPL1, C1(0.000-0.488), C2(0.000-0.000) Background: White Mean  Method: C1 * Mean + C2  Pause On Run 003 InvertBPL1 -> BPL2 004 Pause Edit Line BPL3  measure wires!! 005 (BPL2 ANDBPL3) -> BPL6 006 Object Transfer BPL6 -> None  String Length less than0.005μm 007 Object Measures (BPL6) -> OBJM1  String Length  Aspect Ratio String Length Squared 008 Clear => All 001 Edit Analysis Properties Endof Field 001 Generate Report (should be used in Epilog only)  ReportTemplate: C:\Clemex\templates\width.XLT  Save Report: To“C:\Clemex\Width Analyses\<<Sample>>.xls”  Overwrite Protection: Yes Print Report: No  Close Report: No 002 Save Analysis Results to‘WidthData.cxr’  Destination: C:\Clemex\Width Analyses\Clemexfiles\Width Data.cxr  Overwrite Protection: Yes  Close after Saving: NoEnd of Epilog

To measure the widths, the outlines of all the nanowires in an image arefirst automatically highlighted. A user may manually adjust the relativegray threshold on each image to ensure that the nanowires are accuratelyhighlighted prior to analysis. The user may also select and mark eachindividual wire to be measured. Clemex software (or other suitablesoftware tools) will then collect all the analyzed data and producestatistical report containing all key data (including mean diameter andstandard deviation, and mean diameter squared, and binned distributionof diameters).

The various embodiments described herein are further illustrated by thefollowing non-limiting examples.

EXAMPLES Example 1 Multi-Phase Synthesis of Silver Nanowires

Silver nanowires that conform to certain size distribution profiles weresynthesized in a two-phase process.

A solution of silver nitrate (AgNO₃) was first prepared by mixing 6grams of AgNO₃ in 37 grams of propylene glycol (14% w/w).

445 grams of propylene glycol and 7.2 grams of polyvinylpyrrolidone wereadded to a reaction vessel, which was then heated to 90° C. After themixture in the reaction vessel has stabilized at 90° C., the atmospherein the headspace of the reaction vessel is purged with nitrogen for atleast 5 minutes before the silver nitrate is added.

In the first phase of the reaction, half of the total silver nitrate wasused. Thus, to the heated reactor, 0.6% of the silver nitrate solutionand 1.18 grams of tetra-n-butylammonium chloride hydrate in propyleneglycol (10% solution) were added sequentially, followed by 49.4% of thesilver nitrate solution. The reaction was allowed to run for 12-16hours.

In the second phase of the reaction, the axial growth was predominantwhile the radial growth was effectively arrested. The remaining 50% ofsilver nitrate solution was gradually added while maintaining asubstantially constant concentration of silver ions (over a period of 8hours). The reaction was allowed to run for up to a total of 24 hours,during which time the nitrogen purge was maintained. At the completionof the reaction, the reaction mixture was quenched with 100 grams ofdeionized (DI) water.

The reaction could be carried out in ambient light (standard) or in thedark to minimize photo-induced degradation of the resulting silvernanowires.

Example 2 Purification of Silver Nanowires

The crude product of Example 1 included crude liquids (e.g., reactionsolvents, DI water, reaction by-products), as well as the nanowiresformed. A small amount of nanoparticles and nanorods were also present.

The crude product was collected into closed sedimentation containers andallowed to sediment for 4 to 20 days. Following sedimentation, the crudeproduct separated into supernatant and sediment. The sediment containspredominantly silver nanowires, while the crude liquid, nanorods andnanoparticles remained in the supernatant.

The supernatant was removed and the sediment was re-suspended in DIwater and rocked on a rocker table to facilitate mixing. For finalresuspension, repeated pipetting was used.

FIG. 4 shows the effect of purification on the diameter distribution.Both the crude nanowires and purified nanowires follow a substantiallynormal distribution. The purification process removed nearly allnanowires of 15 nm or less in diameter. The purified nanowires also havea smaller spread or variations around the mean value of the diameters.

Example 3 Determination of Length Distribution

Three batches of silver nanowires were prepared and purified accordingto Examples 1 and 2. A sample of nanowires was randomly collected fromeach batch. The nanowire lengths in each sample were measured andanalyzed using an optical microscope and Clemex softwares, as describedherein. Table 1 shows the size distributions of nanowires prepared inthe three batches.

TABLE 1 Bin range (μm) Batch 1 Batch 2 Batch 3 0-5 7.6% 2.1% 4.3%  5-1012.6% 12.3% 14.6% 10-15 28.8% 35.5% 31.2% 15-20 26.2% 26.2% 25.9% 20-2515.1% 14.0% 14.6% 25-30 5.7% 6.7% 5.9% 30-35 2.1% 2.0% 2.1% 35-40 1.0%0.8% 0.8% 40-45 0.5% 0.2% 0.2% 45-50 0.2% 0.2% 0.2% 50-55 0.1% 0.1% 0.1%55-60 0.0% 0.0% 0.1% 60-65 0.0% 0.0% 0.0%

FIG. 5 further illustrates the size distribution profiles of the threebatches of silver nanowires as log normal distributions. It isdemonstrated that reproducible size distribution profiles were obtainedin nanowires prepared according to the synthesis and purificationprocesses described herein.

The statistics of the lengths are summarized in Table 2.

TABLE 2 Batch 1 Batch 2 Batch 3 Mean <1> (μm) 15.7 16.1 15.8 <1²> (μm²)305 304 300 Minimum (μm) 0.6 0.6 0.6 Maximum (μm) 77.3 51.0 55.6 90^(th)percentile (μm) 24.8 25.0 24.7 95^(th) percentile (μm) 28.5 28.0 28.2count 5899 1745 3710

Example 4 Determination of Diameter Distribution

A sample of nanowires was randomly collected from each batch todetermine their diameter distribution. The nanowire widths in eachsample were measured and analyzed using SEM and Clemex softwares, asdescribed herein Table 3 shows the diameter distributions of nanowiresprepared in three different batches.

TABLE 3 Bin range (nm) Batch 1 Batch 2 Batch 3 0-5 0.0% 0.0% 0.0%  5-100.0% 0.0% 0.0% 10-15 0.0% 0.0% 0.0% 15-20 0.5% 2.2% 0.6% 20-25 11.4%16.2% 20.2% 25-30 45.5% 45.9% 46.2% 30-35 32.7% 27.0% 24.9% 35-40 7.9%6.5% 8.1% 40-45 2.0% 2.2% 0.0% 45-50 0.0% 0.0% 0.0% 50-55 0.0% 0.0% 0.0%55-60 0.0% 0.0% 0.0%

FIG. 6 further illustrates the diameter distribution profiles of thethree batches of silver nanowires as normal or Gaussian distributions.It is demonstrated that reproducible diameter distribution profiles wereobtained in nanowires prepared according to the synthesis andpurification processes described herein.

The statistics of the diameters, including the standard deviations aresummarized in Table 4.

TABLE 4 Batch 1 Batch 2 Batch 3 Mean <d> (nm) 29.7 29.0 28.6 Stdev (nm)4.3 4.5 4.3 <d²> (nm²) 902 860 837 Minimum (nm) 18.7 18.7 19.7 Maximum(nm) 42.4 44.9 39.9 90^(th) percentile (nm) 34.9 34.6 34.5 95^(th)percentile (nm) 37.4 36.2 36.7 Count 202 185 173

Example 5 Preparation of Transparent Conductors

From each batch of silver nanowires prepared according to Examples 1 and2, an ink composition was formulated to include, by weight, 0.1-0.2%silver nanowires, 0.2-0.4% high purity HPMC, and 0.005-0.025% TritonX-100 in DI water. The ink composition was then spin coated on a glasssubstrate to form thin films. More specifically, the samples were spincoated at a speed between 400 to 2000 rpm in 60 seconds, with anacceleration of 1000 rpm/s. The films were subsequently baked for 90seconds at 50° C. followed by 90 seconds at 140° C.

By adjusting the loading amount, spin speed and time, a series of thinfilms were prepared based on the ink compositions of each batch.

Example 6 Transparent Conductor Specifications

The resistance, transmission and haze data for the thin films in eachbatch are summarized in Tables 5-7. The haze and transmission of bareglass (0.04% H and 93.4% transmission) were not subtracted.

TABLE 5 Batch 1 R (ohm/sq) % H % T 32 1.29% 91.4% 56 0.85% 92.1% 880.62% 92.5% 122 0.48% 92.7% 164 0.39% 92.9% 224 0.33% 93.0% 275 0.31%93.0%

TABLE 6 Batch 2 R (ohm/sq) % H % T 34 1.39% 91.1% 52 0.95% 91.8% 680.73% 92.2% 99 0.53% 92.5% 163 0.38% 92.8% 238 0.32% 92.9% 340 0.29%93.0%

TABLE 7 Batch 3 R (ohm/sq) % H % T 38 1.16% 91.7% 87 0.61% 92.5% 1200.50% 92.7% 164 0.40% 92.9% 203 0.37% 93.0% 254 0.33% 93.0%

All of the films showed less than 1.5% haze, while maintaining hightransmission and conductivity. In particular, films having lower than0.4% haze and less than 350 ohm/sq in resistance were obtained.

Further, FIG. 7 shows the inverse correlation of the haze and theresistance of the thin films. It can be observed that as the resistanceincreases (i.e., fewer nanowires are present), the haze value decreasesdue to less scattering.

FIG. 8 shows the positive correlation of the transmission and theresistance of the thin films. It can be observed that as the resistanceincreases (i.e., fewer nanowires are present), the transmissionincreases.

Example 7 Evaluation of Optical and Electrical Properties of TransparentConductors

The transparent conductive films prepared according to the methodsdescribed herein were evaluated to establish their optical andelectrical properties.

The light transmission data were obtained according to the methodologyin ASTM D1003. Haze was measured using a BYK Gardner Haze-gard Plus. Thesheet resistance was measured using a Fluke 175 True RMS Multimeter orcontact-less resistance meter, Delcom model 717B conductance monitor. Amore typical device is a 4 point probe system for measuring resistance(e.g., by Keith ley Instruments).

The haze and transmission of the bare substrate (e.g., 0.04% haze and93.4% transmission for glass) were typically included in themeasurements.

The interconnectivity of the nanowires and an areal coverage of thesubstrate can also be observed under an optical or scanning electronmicroscope.

All of the above U.S. patents, U.S. patent application publications,U.S. patent applications, foreign patents, foreign patent applicationsand non-patent publications referred to in this specification and/orlisted in the Application Data Sheet, are incorporated herein byreference, in their entirety.

From the foregoing it will be appreciated that, although specificembodiments of the invention have been described herein for purposes ofillustration, various modifications may be made without deviating fromthe spirit and scope of the invention. Accordingly, the invention is notlimited except as by the appended claims.

1.-17. (canceled)
 18. A method, comprising: growing metal nanowires froma reaction solution comprising a metal salt and a reducing agent,wherein the growing comprises: reacting a first portion of the metalsalt and the reducing agent in the reaction solution for a first periodof time, and adding a second portion of the metal salt over a secondperiod of time while maintaining a substantially constant concentrationof less than 0.1% w/w of the metal salt in the reaction solution. 19.The method of claim 18, wherein the metal nanowires are silver nanowiresand the metal salt is silver nitrate.
 20. The method of claim 19,wherein the reducing agent is at least one of propylene glycol orethylene glycol.
 21. The method of claim 20, wherein the reactionsolution further comprises at least one of polyvinylpyrrolidone ortetra-n-butylammonium chloride.
 22. The method of claim 18, wherein aratio of the first portion of the metal salt to the second portion ofthe metal salt is between 30-70:70-30.
 23. The method of claim 18,wherein the first period of time is 12-16 hours.
 24. The method of claim18, wherein reacting the first portion of the metal salt and thereducing agent in the reaction solution for the first period of timecomprises: adding a fraction of the first portion of the metal salt withan ammonium salt; and adding a remainder of the first portion of themetal salt.
 25. The method of claim 24, wherein the fraction is selectedsuch that a concentration of metal ions in the reaction solution is0.001% w/w to 0.025% w/w.
 26. The method of claim 24, wherein thefraction is less than or equal to 1% of a combination of the firstportion and the second portion of the metal salt
 27. The method of claim18, comprising: quenching the reaction solution with de-ionized waterafter the second period of time has lapsed to halt growth of the metalnanowires.
 28. The method of claim 18, comprising: purging a reactionvessel comprising the reaction solution with an inert gas while growingthe metal nanowires.
 29. The method of claim 18, wherein the firstportion of the metal salt and the second portion of the metal salt areequal.
 30. The method of claim 18, comprising: combining the metalnanowires and a fluid to form an ink composition, wherein aconcentration of the metal nanowires in the ink composition is 0.01% w/wto 1.5% w/w.
 31. The method of claim 30, wherein: a diameterdistribution of the metal nanowires in the ink composition has astandard deviation that is less than 20% of a mean diameter of the metalnanowires in the ink composition, and more than 99% of the metalnanowires in the ink composition with aspect ratios of at least 10 areno more than 55 μm long.
 32. The method of claim 18, comprising:performing sedimentation on the reaction solution after the secondperiod of time has lapsed to separate the reaction solution intosupernatant and sediment.
 33. A method, comprising: growing metalnanowires from a reaction solution comprising a metal salt and areducing agent, wherein the growing comprises: reacting a first portionof the metal salt and the reducing agent in the reaction solution for afirst period of time to grow the metal nanowires in an axial directionand a radial direction, and adding a second portion of the metal saltover a second period of time, wherein, during the second period of time,the metal nanowires grow in the axial direction.
 34. The method of claim33, wherein growth of the metal nanowires in the radial direction isstopped during the second period of time.
 35. The method of claim 33,wherein reacting the first portion of the metal salt and the reducingagent in the reaction solution for the first period of time comprises:adding a fraction of the first portion of the metal salt with anammonium salt; and adding a remainder of the first portion of the metalsalt.
 36. A method, comprising: growing metal nanowires from a reactionsolution comprising a metal salt and a reducing agent using a two-phasesynthesis process in which a concentration of the metal salt in thereaction solution is maintained at less than 0.1% w/w during a secondphase of the two-phase synthesis process.
 37. The method of claim 36,wherein the reducing agent is at least one of propylene glycol orethylene glycol.